Method of dyeing vinyl polymers



. Patented Jan. 20, 1942 UNITED STATES PATENT OFFICE Manon or Brig own mamas Karl HeymanmMeadviiie, Pm, alaignor to American Viscose Corporation, Wilmington, 'DeL, a corporation of Delaware No Drawing. min-mm]. 11, 1940,

Serial No. seam 4 Claims. ((18-35) ThL'. invention relates to improvements in methods of dyeing yarns and other shapes comwater can not be satisfactorily dyed by the ordinary dyeing procedure used in dyeing cotton, wool, natural silk and regenerated cellulose.

' When ordinary methods of dyeing are. attempted the dye either does not penetrate the material and no dyeing is effected or when dyeing is efiected the color is not fast and leaches out.

Yarns and other shapes of cellulose acetate which are not readily permeable to water have been dyed when treated with a liquid swelling agent, such as alcohol; acetone or acetic acid. The swelling agent forms or openspores in the material into which the dye penetrates- There 'are certain objections to the useot liquid swelling agents. Generally a' large amount of swelling agent is required.v Also the swelling agent has i a tendency to weaken the yarn or.shape. I have discovered that yarns and other shapes comprising vinyl polymers, such as polymers of vinyl chloride and copoiymers of vinyl acetate and vinyl chloride can be successfully dyed with ension dyestuffs when the dyeing operation is carried out in the presence of suspensions of certain normally sclld organic compounds which have a solubility in polymers of vinyl chloride and copolymers of vinyl acetate and vinyl chloride of 2% or greater under the conditions at which the dyeing is carried out. 'By the term 8-hydroxyquinoline Dibenzyi succinate liIethyl-p-bromohenzoute Dishenyl phthalate baphthvl acetate Phenyl iycine ethylester Dipheny carbonate Di-o-cresyl carbonate 2,4,6 tribromophenyl acetate Phen l-bnaphthylamine o-Am nodiphenyl pI-Aminodiphenyl i ,Nt-diphenyl ethyl carbam- 8 e i b-Na hthonitriie g-Ch orobenzaidehyde ,4-dimethoxybenzaldehyde p LDdimethyIaminoDenzaIdey e a-Naphthyl acetate o-Hydroxyacetophenone a o-Diphenyl acetate Benzophenone Ethylene dibenzoate. D-Hvdroxybenzophenone Glycerol tribenzoate Methyl-'b-naphthylketone Dicyclohexlyli phthalate Camphor Dibenzyl p thalate Benzalacetpne Phenyl benzoate Anisalacetone m-Cresyl benzoate Benzo lacetone Benza acetophenone 1-hvdroxy-2-acetonaphthone -li etlhoxybenzophenone -Cresyl benzoate enzh drol Pheny benzylcarbinoi Fiuoren 1 alcohol en b,b-Dip enox diethylethcr Diphenyltriketone. p-Methoxydip enyl Dibeuloylmethane Benzyl-a-naphthylether Desoxybenzoin b-Naphthylmethylether Fiuorenone Benzoic anhydridc In carrying out myimproved method'of dyeing a suspension of a single assistant or several assis'tants together may be used. The assistant is,

for example, dissolved in a suitable solvent, such as alcohol, and the assistant in solution and a suitablev dispersing agent, such as that known in the'trade as Igepon T, are added to the dye bath. The dye bath containsa suspension ,dyestuif. The'assistant is precipitated in the dye bath in colloidal or very finely divided form. When amino compounds are used as assistants they may be dissolved in an acid solution and precipitated and dispersed in an alkaline dye bath.

Phenolsmay be dissolved in an alkaline solution and precipitated and dispersed in an acid dye bath. Satisfactory results are also obtained under certain conditions when the phenol solution is added to the dye bath and is not dispersed. The yarn or shape to be dyed is treated with the dye bath containing the assistant in the ordinary suspension dyestuifs is meant dyestuffs of the i type applicable to cellulose acetate from a dispersion (insoluble anthraquinone and azo dyes) sometimes referred to as dispersol dyes, and the dyestuils referred to hereinafter in the examples by their trade names, are of this type. The compounds which are referred to as assistants include:

' hen l 2- ciiloro-o-phenylphenoi l phthiiene 4 chioroo-phenyiphenoi Phenanthrene o-Cgclohexyiphenol a-Naphtbol g'C lorothymoi lrNapbthol ,4-dichloroaniline Thio-baapbthol 2,5-dichloroaniilne 2,4 dichioro-a-naphthoi a-Naphthylamine 2.4-dibromo-a-naphthoi irNaphthylamine o-Hydroxydiphenyi ihenyl-a'naphthylamine dye baths depending upon the character of the manner.

This procedure may be followed using various quantities or ,dyestuil and assistants with different dye bath ratios and temperatures of the material beingdyed and the type of dyeing that is being carried out. A satisfactory procedure is one in which the dye bath ratio is 1:30 and contains 1.5% suspension dyestuil with 5% or less of assistant based on the weight of the yarn or shape to be dyed. A suitable dye bath temperature is about 50" C. and the duration oi the dyeing operation one hour. Other temperatures may also be used. 7

My invention 'may also be carried out by applying the'assistant from suspensiondirectly to the yarn or shape. When the yarn or shape is there- 55 after immersed in the dye bath the assista t aids the action of the dye bath on the yarn or shape in the same manner as when it has been added j. bath wasalso to the dye bath.

Instead of using either of the above methods. I mayadd the assistant directly to thevinyl polymers before the yam'or shape is formed. The

yarn or shape containing the assistant is treated with the dye b th in theordinary manner. I a The following examples are illustrative of the invention: 7 q Example Ir -Yams comprising copolymers of vinyl acetate and vinyl chloride were dyed in dye dyestufls were were I 1. .Cibaoete OrangeflBR I tCibacete ScarletG. f i 'M m ,acei yeuowisiq r q 1%and Ace'1e Violet-B 1%,asth dyestufl. Example .2. '-Yarns comprising copolymer of yinyl acetatelandf vinyl "chloride were dyed in dye baths-having a dye'bath ratio-: 1:30 and containing suspension;dye'sti1ii'and5% p di-f i methylamind-benzaldehydebased on the weight oi the min. The temperatures or the dye baths were 60 C. and the duration oithe dyeing opwith Cibacete Scarlet .bathshaving-a dyaflbathratio ot;1:30 and'containing 1,35% suspension dyestuiifand 5% b naph- [thol basedfon the weight oi theyam. 'Thetem- 1 e peratures oi thedyebaths were 60 C. and "the duration 01 the dyeing operation one-hour. The

and the duration or the dyeing operation one hour. The dyestuffs that were use were Celliton Pink RF 7 Celliton Red BP 1 Celliton Orange 3RN Cibacete Yellow 2RN Celliton Fast Yellow GRA Cibacete Yellow 5G CibaceteBrill. Blue BGG Celliton Fast Blue F'FRS Celllton Discharge VioletB Cibacete Dischargeviolet 5R Carnacyl Brill. Green B Phenacyl Red R Qibacete Violet B Artisil Direct Yellow 3GP ex. cone. '1 Celllton Fast Brown BRA Eaample 5.-Yarns comprising copolymers of vinyl acetate and vinyl chloride were treated with a bath in a ratio of 1:30 containing 5% o-hydroxydiphenyl based on'theweight of the yarn at a temperaturebi60 C. and for a; period of oneeration one hour. The dyes-tune that were used 1 were i 1;

. CellitonRed'VioletRR Bhena'cyl NavyBluePV {Phenaoyl'Red'RiJ-i"r i CelutateBrilLBlue B T ibi ie b n 'Bs Y .rtisilDifet Yellow 3G1? Thetemperatures of the dye baths .were 60- C.

40 r A a lined in the appended claims. mprisingflcopolymers of n'y chloride 'were dyed: in

or shape with a dye bath. containing a suspension half hour. The yarns so treated were then dyed 'byimmersing'in dye baths having a dye bath ratio of 1:30 and containing 1.5% suspension dyestui! basedon the weight of the, yarn. The

temperatures of the dye baths were C. and i the duration of the dyeing operation one hour.

- The dyestufis that were used were I Camacyl Brill. Green B -Phenacyl Red R CibaceteViolet B Artisil Direct Yellow 3GP ex. conc. Celliton Fast Brown 53A i While preferred assistants and procedures have been-{shown itis to be understood that changes and variations may be made without departing tromthe spirit and scope or the invention as de- WhatI claim is:

1. A. method 01- dyeing yarns and other shapes comprising vinyl polymers, comprising the step of treating the yarn or shape with a dye bath containinga suspension 'dyestufl in the presence of 8-hydroxyquinoline.

2. A method 0! dyeing yarns and other shapes comprising copolymersoi vinyl acetate and vinyl chloride, comprising the step, or treating the yarn dyestufl in thepresence of 8-hydroxyquinoline.

iii

. 3. A method of dyeingyarns and other shapes comprising 1'vinyl polymers, comprising the step of, treating the yarn or-shapewith .a dye bath containing a suspension dyestuffand -8-hydroxyquinoline.

. vinyl acetate-and vinyl chloride were dyed indye Y "baths having adyebath ratio 011:30 and con:

- taining 1 .5% suspension dyestui! and 5% o-hydroxydiphenyl'based on the. weight or the yarn;

4. A method of dyeing and other shapes comprising .copolymers of vinyl acetate and vinyl chloride, comprising thestep of treating the yarn or shape with a dye bath containing a suspension dyestufiand 8-hydroxyquinoline.

i KARLHEYMANNH 

